Use of rection products of Homo- or copolymers based on monoethylenically unsaturated dicarboxylic anhydrides with amines or alcohols for fatliquoring and filling leather and fur skins

ABSTRACT

Products useful for fatliquoring and filling leather and fur skins are obtained on reacting 
     A) homo- or copolymers based on monoethylenically unsaturated dicarboxylic anhydrides and obtainable by free-radically initiated polymerization of 
     a) from 30 to 100 mol % of one or more monoethylenically unsaturated dicarboxylic anhydrides of from 4 to 10 carbon atoms, 
     b) from 0 to 70 mol % of one or more aromatic vinyl compounds of the general formula I ##STR1##  where R 1 , R 2  and R 3  are each hydrogen, methyl or ethyl and k is 1 or 2, 
     (c) from 0 to 70 mol % of one or more vinyl esters of C 1  - to C 8  -carboxylic acids, 
     (d) from 0 to 50 mol % of one or more C 2  - to C 6  -olefins, and 
     (e) from 0 to 30 mol % of one or more monoethylenically unsaturated C 3  - to C 5  -carboxylic acids, 
      which mixture of monomers (a) to (e) may additionally contain up to 10% by weight of further copolymerizable monomers, with 
     B) amines of the general formula R 4  R 5  NH, where R 4  is hydrogen, C 1  - to C 20  -alkyl, C 5  - to C 8  -cycloalkyl or C 2  - to C 4  -hydroxyalkyl and R 5  is C 6  - to C 30  -alkyl, C 6  - to C 30  -alkenyl, C 5  - to C 8  -cycloalkyl or C 2  - to C 4  -hydroxyalkyl, or alcohols of the general formula R 6  --O--(C m  H 2m  O) p  --(C n  H 2n  O) q  --H, where R 6  is C 1  - to C 30  -alkyl, C 2  - to C 30  -alkenyl, C 5  - to C 8  -cycloalkyl or--if p+q&gt;0--hydrogen, m and n are each from 2 to 4 and p and q are each from 0 to 50, or mixtures of such amines and alcohols.

The present invention relates to the use of reaction products of homo-or copolymers based on monoethylenically unsaturated dicarboxylicanhydrides with amines and alcohols for fatliquoring and filling leatherand fur skins. The invention also relates to leather treatmentcompositions containing these reaction products.

To control the mechanical properties of leather, such as softness,flexibility or suppleness, it is common practice to employ aqueous fatemulsions (fat liquors) which are generally based on petrochemicallyproduced or natural oils and fats. These oils and fats are in generalrendered emulsifiable in water by partial sulfonation or by means ofemulsifiers. Disadvantages of this class of fatliquoring agents areincomplete liquor exhaustion, relative ease of extraction by solvents orwater, the occurrence of migration phenomena and unsatisfactory fastnessprofiles.

Polymeric products, based for example on unsaturated dicarboxylic acidderivatives and long chain olefins, that have fatliquoring propertiesfor leather and fur skins are known and find utility as water repellentsfor leather and fur skins.

For instance, EP-A-412 389 recommends the use as water repellents forleather and fur skins of copolymers of C₈ - to C₄₀ -monoolefins andethylenically unsaturated C₄ - to C₈ -dicarboxylic anhydrides, convertedinto aqueous solutions or dispersions by solvolysis of the anhydridegroups, for example with bases such as amines, or partial esterificationof the anhydride groups with alcohols and at least partialneutralization of the resulting carboxyl groups with bases in an aqueousmedium.

Polymeric fatliquoring agents of this type do have some effect, but theyare not entirely satisfactory for soft kinds of leather. Soft leathersrequire an additional, native or synthetic fat liquor that complementsthe action of the polymeric agent.

It is an object of the present invention to provide an improvedfatliguoring and filling agent for leather and fur skins that is free ofthe prior art disadvantages.

We have found that this object is achieved by using reaction products of

A) homo- or copolymers based on monoethylenically unsaturateddicarboxylic anhydrides and obtainable by free-radically initiatedpolymerization of

a) from 30 to 100 mol % of one or more monoethylenically unsaturateddicarboxylic anhydrides of from 4 to 10 carbon atoms,

b) from 0 to 70 mol % of one or more aromatic vinyl compounds of thegeneral formula I ##STR2## where R¹, R² and R³ are each hydrogen, methylor ethyl and, k is 1 or 2,

(c) from 0 to 70 mol % of one or more vinyl esters of C₁ - to C₈-carboxylic acids,

(d) from 0 to 50 mol % of one or more C₂ - to C₆ -olefins, and

(e) from 0 to 30 mol % of one or more monoethylenically unsaturated C₃ -to C₅ -carboxylic acids,

which mixture of monomers (a) to (e) may additionally contain up to 10%by weight of further copolymerizable monomers, with

B) amines of the general formula R⁴ R⁵ NH, where R⁴ is hydrogen, C₁ - toC₂₀ -alkyl, C₅ - to C₈ -cycloalkyl or C₂ - to C₄ -hydroxyalkyl and R⁵ isC₆ - to C₃₀ -alkyl, C₆ -to C₃₀ -alkenyl, C₅ - to C₈ -cycloalkyl or C₂ -to C₄ -hydroxyalkyl, or alcohols of the general formula R₆ -Q-(C_(m)H_(2m) O)_(p) -(C_(n) H_(2n) O)_(q) -H, where R⁶ is C₁ - to C₃₀ -alkyl,C₂ - to C₃₀ -alkenyl, C₅ - to C₈ -cycloalkyl or--if p+q>0--hydrogen, mand n are each from 2 to 4 and p and q are each from 0 to 50, ormixtures of such amines and alcohols,

for fatliquoring and filling leather and fur skins.

Suitable monoethylenically unsaturated dicarboxylic anhydrides of from 4to 10 carbon atoms (a) are in particular maleic anhydride, itaconicanhydride, citraconic anhydride, mesaconic anhydride, methylenemalonicanhydride and mixtures thereof. Maleic anhydride is particularlypreferred.

In the general formula I for the aromatic vinyl compounds (b), R¹ ispreferably hydrogen or methyl, R² and R³ are each preferably hydrogenand k is preferably 1. If when k is 1 R³ is methyl or ethyl, it ispreferably in the para position. If when k is 2 R³ is methyl or ethyl,the substitution pattern on the phenyl is preferably 2,4.

Suitable aromatic vinyl compounds (b) are in particular styrene,α-methylstyrene and a mixture thereof.

Suitable vinyl esters (c) are in particular vinyl esters of C₁ - to C₄-carboxylic acids, e.g. vinyl formate, vinyl propionate, vinyl butyrateor in particular vinyl acetate. Mixtures of such vinyl esters can alsobe used.

Suitable C₂ - to C₆ -olefins (d) are in particular straight-chain orbranched monoolefins, in particular α-olefins, e.g. ethylene, propylene,1-butene, isobutene, 1-pentene or 1-hexene, also 2-butene, 2-pentene,2-hexene or 3-hexene. Isobutene is particularly preferred. It is alsopossible, however, to use conjugated dienes such as butadiene orisoprene. Similarly, mixtures of said olefins can be used.

Suitable monoethylenically unsaturated carboxylic acids (e) are inparticular C₃ - or C₄ -carboxylic acids, e.g. crotonic acid or inparticular acrylic acid and methacrylic acid.

Useful products are homopolymers A of a monomer (a), copolymers A of twoor more monomers (a) and copolymers A of monomers (a) to (e), in whichcase, however, the copolymer must contain at least 30 mol % ofmonoethylenically unsaturated dicarboxylic anhydride (a). For instance,a useful copolymer composition is 60 mol % of styrene, 30 mol % ofmaleic anhydride and 10 mol % of acrylic acid, or else 50 mol % ofmaleic anhydride, 25 mol % of styrene and 25 mol % of vinyl acetate.

In a preferred embodiment, component A in the preparation of thereaction products used according to the invention is a homopolymer of amonoethylenically unsaturated dicarboxylic anhydride of from 4 to 10carbon atoms (a).

In a further preferred embodiment, component A in the preparation of thereaction products used according to the invention is a copolymer of

(a) from 30 to 99 mol % of a monoethylenically unsaturated dicarboxylicanhydride of from 4 to 10 carbon atoms, and

(b) from 1 to 70 mol % of one or more aromatic vinyl compounds I.

In a further preferred embodiment, component A in the preparation of thereaction products used according to the invention is a copolymer of

(a) from 30 to 99 mol % of a monoethylenically unsaturated dicarboxylicanhydride of from 4 to 10 carbon atoms, and

(c) from 1 to 70 mol % of one or more vinyl esters of C₁ - to C₈-carboxylic acids.

In a further preferred embodiment, component A in the preparation of thereaction products used according to the invention is a copolymer of

(a) from 50 to 99 mol % of a monoethylenically unsaturated dicarboxylicanhydride of from 4 to 10 carbon atoms, and

(d) from 1 to 50 mol % of one or more C₂ - to C₆ -olefins.

To achieve further modification of the properties of the polymers A itis possible to use in addition small amounts of further monomerscopolymerizable with the monomers (a) to (e), in particularmonoethylenically and polyethylenically unsaturated compounds. These arefor example hydroxyalkyl esters having from 2 to 6 carbon atoms in thealkyl moiety and the corresponding nitriles of the aforementioned mono-and dicarboxylic acids, N-vinylamides such as, for example,N-vinylacetamide, N-vinylpyrrolidone, N-vinylpiperidine,N-vinylcaprolactam, N-vinylsuccinimide, N-vinylphthalimide,N-vinyloxazolone, N-vinylformamide and N-vinylimidazole and also alkylvinyl ethers having from 1 to 18 carbon atoms in the alkyl moiety, forexample methyl vinyl ether, ethyl vinyl ether or stearyl vinyl ether,and C₈ - to C₃₀ -olefins, in particular C₁₀ - to C₂₀ -α-olefins, forexample 1-dodecene, 1-hexadecene or 1-octadecene. Also suitable aremethylenebisacrylamide, esters of acrylic acid, methacrylic acid andmaleic acid with polyhydric alcohols, for example glycol diacrylate,glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate,and also at least doubly acrylated or methacrylated polyols such aspentaerythritol and glucose. It is also possible to use divinylbenzene,divinyldioxane, pentaerythritol triallyl ether, pentaallylsucrose andalso glycol diacrylates of polyethylene glycols having molecular weightsup to 3000. These modifying monomers for the polymers A are added to themonomer mixture of (a) to (e) in amounts of up to 10% by weight,preferably up to 5% by weight.

The polymers A can be prepared by conventional free radicalpolymerization. Especially the techniques of suspension, solution andbulk polymerization can be employed. Examples of diluents or solventsused for the polymerization are organic solvents such as toluene,xylene, ethylbenzene, isopropylbenzene, tetrahydrofuran, dioxane,cyclohexane, petroleum ethers or naphtha. The reaction is carried outunder atmospheric or super-atmospheric pressure. Suitable free radicalinitiator systems are all those which form free radicals under thedesired polymerization conditions, for example di-tertbutyl peroxide,tert-butyl perbenzoate or tert-butyl perethylhexanoate. It is possible,in particular in the case of suspension polymerization, to addprotective colloids such as polyethyl vinyl ether.

The K values of the polymers A are in general within the range from 6 to200, in particular from 8 to 100. The K values of the copolymers weredetermined by the method of Fikentscher on 1% strength by weightsolutions in cyclohexanone and the K values of the homopolymers (a) indimethylformamide as solvent at 25° C.

The as-synthesized polymers A can be isolated in the solid form, driedif desired, and then reacted with component B. However, the polymers Acan also be reacted directly in solution with component B.

Suitable alcohols of component B for reaction with the polymers A are inparticular primary, secondary and tertiary alcohols of from 1 to 30carbon atoms. It is possible to use not only saturated aliphaticalcohols but also unsaturated alcohols, for example oleyl alcohol.Preference is given to primary or secondary alcohols, e.g. amyl alcohol,n-hexanol, n-octanol, 2-ethylhexanol, n-nonanol, isononanol, n-decanol,n-dodecanol, n-tridecanol, isotridecanol, cyclohexanol, naturallyoccurring fatty alcohols such as tallow fat alcohol or stearyl alcoholand also the industrially readily obtainable oxo process alcohols oralcohol mixtures of from 9 to 19 carbon atoms, for example C_(16/10) oxoalcohol, C_(13/15) oxo alcohol, and also Ziegler alcohols of from 12 to24 carbon atoms, e.g. C_(12/14) or C_(16/18) cuts.

The alcohols of component B can also be present as alkoxylates, ie. asreaction products with a C₂ - to C₄ -alkylene oxide such as ethyleneoxide, propylene oxide or butylene oxide. In this case the molecule maycontain one or two different alkylene oxide blocks. A suitable alkyleneunit for such a block also includes tetramethylene as thepolytetrahydrofuran structure.

Other suitable alcohols for use as component B are ether alcohols andpolyetherdiols such as ethylene glycol monobutyl ether, di- andtriethylene glycol monobutyl ether, polytetrahydrofuran and alsopolyethylene glycols and polypropylene glycols.

In a preferred embodiment, component B in the preparation of thereaction products used according to the invention comprises alcoholswhere R⁶ is C₁ - to C₂₂ -alkyl or C₁₀ - to C₂₂ -alkenyl, m and n areeach from 2 to 4 and p and q are each from 0 to 35.

Suitable primary or secondary amines of component B for reaction withthe polymers A are for example n-hexylamine, cyclohexylamine,methylcyclohexylamine, 2-ethylhexylamine, n-octylamine, n-tridecylamine,isotridecylamine, tallow fat amines, stearylamine, oleylamine,di-n-hexylamine, dicyclohexylamine, di(methylcyclohexyl)amine,di(2-ethylhexyl)amine, di(n-octyl)amine, di(isotridecyl)amine,ditallowamine, distearylamine, dioleylamine, diethanolamine,di-n-propanolamine and diisopropanolamine.

In a preferred embodiment, component B in the preparation of thereaction products used according to the invention comprises amines whereR⁴ is hydrogen and R⁵ is C₁₀ - to C₂₂ -alkyl or C₁₀ - to C₂₂ -alkenyl.

The reaction of polymers A with the amines or alcohols B is carried outin a conventional manner and generally involves the introduction ofcarboxylic ester or carboxamide functions into the polymers A. Aminesare advantageously reacted with the polymers A under atmospheric orsuperatmospheric pressure at about 60°-130° C. in the absence of asolvent or in inert organic solvents such as toluene, xylene,cyclohexane, petroleum ether or naphtha customarily present from thepreparation of the polymers A themselves. The reaction of the alcoholswith the polymers A is advantageously likewise carried out in theabsence of a solvent or preferably in inert organic solvents such asthose mentioned above in the presence of acidic catalysts such asp-toluenesulfonic acid under atmospheric or superatmospheric pressure atabout 100°-150° C.

The ratio between the components A and B in the reaction is customarilychosen in such a way that from 0.2 to 1.0 mol of amine or alcohol B or amixture thereof is used per mole of monomer a) within the polymer A.

After the reaction between components A and B has ended, it is customaryto remove any organic solvent present, preferably by distillation, andto disperse the product in an aqueous solution of a base, preferably ofan alkali metal hydroxide such as sodium hydroxide or potassiumhydroxide or ammonia, in order that the remaining anhydride functions ofthe partially esterified or amidated polymers may be partially orcompletely hydrolyzed and partially or completely neutralized.

The polymer dispersions thus obtainable are suitable for treating anyconventional tanned hide. Tanned hides are customarily neutralized priorto the treatment. They may have already been dyed prior to thetreatment. However, dyeing may also be delayed until after thefatliquoring of the invention.

The tanned hides are advantageously treated with the aqueous dispersionsin an aqueous liquor at pH 4-10, preferably pH 5-8, and 20°-60° C.,preferably 30°-50° C., for 0.1-5 hours, in particular 0.5-2 hours. Thistreatment may take the form for example of drumming. The amount ofreaction product of A and B required is, based on the shaved weight ofthe leather or the wet weight of the fur skin, from 0.1 to 30% byweight, preferably from 1 to 20% by weight. The liquor length, ie. thepercentage weight ratio of treatment liquor to goods, based on theshaved weight of the leather or the wet weight of the fur skin, iscustomarily from 10 to 1000%, preferably from 30 to 150%, in the case offur skins from 50 to 500%. The dispersions used of the reaction productsof A and B generally do not contain any additional emulsifiers.

After the treatment with the aqueous liquor described, the pH of thetreatment liquor is adjusted with acids, preferably organic acids suchas formic acid, to pH 3-5, preferably 3.5-4.

If customary retanning agents are additionally employed in the finishingprocess on the leather or fur skin, the treatment with the reactionproducts of A and B to be used according to the invention can be carriedout before or after the retanning operation.

The present invention further provides leather treatment agentscomprising reaction products of

A) homo- or copolymers based on monoethylenically unsaturateddicarboxylic anhydrides and obtainable by free radical polymerization of

a) from 30 to 100 mol % of one or more monoethylenically unsaturateddicarboxylic anhydrides of from 4 to 10 carbon atoms,

b) from 0 to 70 mol % of one or more aromatic vinyl compounds of thegeneral formula I ##STR3## where R¹, R² and R³ are each hydrogen, methylor ethyl and k is 1 or 2,

(c) from 0 to 70 mol % of one or more vinyl esters of C₁ - to C₈-carboxylic acids,

(d) from 0 to 50 mol % of one or more C₂ - to C₆ -olefins, and

(e) from 0 to 30 mol % of one or more monoethylenically unsaturated C₃ -to C₅ -carboxylic acids,

which mixture of monomers (a) to (e) may additionally contain up to 10%by weight of further copolymerizable monomers, with

B) amines of the general formula R⁴ R⁵ NH, where R⁴ is hydrogen, C₁ - toC₂₀ -alkyl, C₅ - to C₈ -cycloalkyl or C₂ - to C₄ -hydroxyalkyl and R⁵ isC₆ - to C₂₀ -alkyl, C₆ -to C₃₀ -alkenyl, C₅ - to C₈ -cycloalkyl or C₂ -to C₄ -hydroxyalkyl, or alcohols of the general formula R⁶ --O--(C_(m)H_(2m) O)_(P) --(C_(n) H_(2n) O)_(q) --H, where R⁶ is C₁ - to C₃₀-alkyl, C₂ - to C₃₀ -alkenyl, C₅ - to C₈ -cycloalkyl or--ifp+q>0--hydrogen, m and n are each from 2 to 4 and p and q are each from0 to 50, or mixtures of such amines and alcohols.

The reaction products to be used according to the invention make itpossible to prepare very soft leather without the addition ofconventional fat liquors. This advantage is reflected in simple andshort application recipes.

As well as improving the mechanical properties such as tensile strengththese polymeric fatliquoring agents bring about a distinct enhancementin the fastness profile of the leather. For instance, they have a verypositive effect on the light fastness and thermal yellowing resistanceof such leathers. In addition to producing a virtually quantitativeexhaustion of the liquor the good fixation in the leather yields greatresistance to extractability with solvents or water. This results inwashable leathers, i.e. leathers which on washing do not lose theirproperties such as softness, firmness and suppleness, unlike leathersfatliquored with conventional fat liquors.

Suitable choice of the specific alcohols and amines of component B inthe reaction products used according to the invention makes it possibleto vary the hydrophobic properties of these polymeric fatliquoringagents in such a way that the leather may also be given a certain waterresistance.

A further advantage of the reaction products used according to theinvention is that dispersions produced therefrom do not require anyadditional emulsifiers for application to leather or fur skin. Leathersand furs treated with emulsifier-containing products must afterwards besubjected in many cases to expensive processes, for exampleaftertreatment with polyvalent metal salts, in order to render theemulsifiers ineffective within the leather or fur skin.

EXAMPLES

The percentages in the examples are by weight, unless otherwise stated.The molecular weights of the copolymers were determined by gelpermeation chromatography using tetrahydrofuran as mobile phase andnarrow fractions of polystyrene for calibration. The Fikentscher Kvalues were determined on 1% strength by weight solutions at 25° C. incyclohexanone in the case of the copolymers and auxiliaries and indimethylformamide instead of cyclohexanone in the case of thehomopolymers of the monomers (a).

Preparation of polymers A

EXAMPLE 1

In a heatable reactor equipped with stirrer, reflux condenser,thermometer, addition means and nitrogen inlet and outlet means 1600 gof technical grade xylene, 392 g (4.0 mol) of maleic anhydride and 7 gof polyethyl vinyl ether having a K value of 50 were heated to the boiland 344 g (4.0 mol) of vinyl acetate and a solution of 4 g ofdi-tert-butyl peroxide in 200 g of technical grade xylene were meteredin under boiling conditions at uniform rates over 2 hours. Thereafterthe reaction mixture was stirred under reflux for one hour and cooled,the finely suspended polymer was filtered off, and the filter cake wasdried to 80° C. under reduced pressure. The K value of the copolymer,present in the form of a white powder, was 15.9, and the molecularweight was 7000.

EXAMPLE 2

In a reactor as in Example 1 1960 g of o-xylene, 441 g (4.5 mol) ofmaleic anhydride and 45 g of polyethyl vinyl ether having a K value of50 were heated to the boil and 468 g (4.5 mol) of styrene and a solutionof 18.2 g of tert-butyl perbenzoate in 162 g of o-xylene were metered inunder boiling conditions at uniform rates over 3 hours. This wasfollowed by further heating for 2 hours and then cooling. The. K valueof the polymer obtained was 14.6 and the molecular weight was 5000. Thelight brown, fine suspension having a polymer content of 29.5% wasdirectly further processible into a leather fatliquoring agent.

EXAMPLE 3

The preparation was carried out similarly to Example 2, except that inthis case 264.6 g (2.7 mol) of maleic anhydride and 655.2 g (6.3 mol) ofstyrene were used. The K value of the polymer obtained was 16.0 and themolecular weight was 9000. The fine, light brown polymer suspension wasdirectly further processible into a leather fatliquoring agent.

EXAMPLE 4

In a reactor as in Example 1 1750 g of maleic anhydride and 1165 g ofo-xylene were heated to the boil and a solution of 262 g of tert-butylperethylhexanoate in 190 g of o-xylene was metered in under boilingconditions at a uniform rate over 5 hours. Thereafter the reactionmixture was heated for a further hour and then the o-xylene was decantedoff the melt, and the melt was poured onto an aluminum tray and cooled.The resin was comminuted and the remaining solvent was distilled offunder reduced pressure. The polymer had a K value of 10 and themolecular weight was 1000.

EXAMPLE 5

A pressure reactor equipped as described in Example 1 was charged with1210 g of o-xylene, 636 g (6.5 mol) of maleic anhydride and 6 g ofpolyethyl vinyl ether having a K value of 50. The reactor was tightlysealed, then injected three times with nitrogen to 3 bar and let downagain each time, evacuated and heated to 120° C. Thereafter 364 g (6.5mol) of isobutene and a solution of 30 g of tert-butyl perethylhexanoatein 250 g of o-xylene were metered in at 120° C. over 4 hours at uniformrates. This was followed by heating at 120° C. for a further 2 hours.Then the pressure, which had built up to 3 bar, was let down and thereactor was cooled. The viscous, finely granular suspension of thecopolymer was stripped of solvent at 80° C. under reduced pressure. Thecopolymer obtained was a fine powder having a K value of 25 and itsmolecular weight was 8000.

Preparation of dispersions of reaction products of A and B

The reaction products of polymers A and amines B were prepared by addingthe a mines specified in the table to the polymers specified in thetable in xylene at from 120° to 130° C. in the molar ratio ofamine:maleic anhydride (MA) in the polymer specified in the table. Afterthe reaction ended, the xylene was distilled off and the product wasdispersed with an Ultraturax stirrer in aqueous sodium hydroxidesolution in the molar ratio of NaOH:MA in the polymer specified in thetable to produce a 20-25% strength dispersion having a pH of from 7 to8.

The reaction products of polymers A and alcohols B were prepared byreaction of the alcohols specified in the table with the polymersspecified in the table in xylene at from 120° to 130° C. in the presenceof catalytic amounts of p-toluenesulfonic acid during 3-5 hours in themolar ratio of alcohol:MA in the polymer specified in the table. Afterthe reaction had ended, the xylene was distilled off and the product wasdispersed with an Ultraturax stirrer in aqueous sodium hydroxidesolution in the molar ratio of NaOH:MA in the polymer specified in thetable to produce: a 20-25% strength dispersion having a pH of from 7 to8.

                                      TABLE                                       __________________________________________________________________________    Dispersions of reaction products of A and B                                      Polymer                                                                            Polymer Amine/Alcohol B NaOH per                                      Ex.                                                                              A of composition                                                                           (mol per mole of                                                                              (mol mole                                     No.                                                                              Ex. No.                                                                            (mol %) MA)             of MA)                                        __________________________________________________________________________     6 1    MA/vinyl                                                                              Tallow fat alcohol                                                                             0.75                                                 acetate 0.75                                                                  50/50                                                                  7 2    MA/styrene                                                                            C.sub.13/15 oxo alcohol                                                                       0.8                                                   50/50   0.25                                                           8 3    MA/styrene                                                                            C.sub.12/14 oxo alcohol                                                                       0.5                                                   30/70   0.3                                                            9 4    MA      Tallowamine      0.75                                                 100     0.5                                                           10 4    MA      Tridecylamine   0.8                                                   100     0.25                                                          11 5    MA/isobutene                                                                          C.sub.13/15 oxo alcohol                                                                       0.5                                                   50/50   0.25                                                          12 5    MA/isobutene                                                                          2-Ethylhexanol  0.5                                                   50/50   0.5                                                           13 1    MA/vinyl                                                                              Oleyl alcohol   0.5                                                   acetate                                                                       50/50   0.4                                                           14 4    MA      CH.sub.3 -O-(C.sub.4 H.sub.8 O).sub.10 H                                                      0.5                                                   100     1.0                                                           15 4    MA      CH.sub.3 -O-(C.sub.4 H.sub.8 O).sub.15 H                                                      0.5                                                   100     0.5                                                           16 4    MA      C.sub.6 B.sub.13 -O--C.sub.2 H.sub.5 O-(C.sub.3 H.sub.6                       O).sub.34 H     0.5                                                   100     1.0                                                           17 1    MA/vinyl                                                                              CH.sub.3 -O-(C.sub.4 H.sub.8 O).sub.9.3 H                                                     0.5                                                   acetate                                                                       50/50   1.0                                                           18 2    MA/styrene                                                                            CH.sub.3 -O-(C.sub.4 H.sub.8 O).sub.5 H                                                       0.5                                                   50/50   1.0                                                           19 5    MA/isobutene                                                                          CH.sub.3 -O-(C.sub.4 H.sub.8 O).sub.10 H                                                      0.5                                                   50/50   1.0                                                           20 2    MA/styrene                                                                            C.sub.4 H.sub.9 -O-(C.sub.2 H.sub.5 O).sub.22 -(C.sub.3                       H.sub.6 O).sub.13 H                                                                           0.5                                                   50/50   0.5                                                           __________________________________________________________________________     Note: C.sub.4 H.sub.8 O in Examples 14, 15, 17, 18 and 19 is oxybutylene,     obtained by reaction of methanol with butylene oxide                     

USE EXAMPLES EXAMPLE 21

Chrome tanned cattlehide leather which had a shaved thickness of 1.8 mmand had been adjusted to a pH of 5.0 was drummed with 15% of the productof Example 6, based on the shaved weight, at 40° C. for 2 hours. Thetotal liquor length was 150%. The leather was then dyed with 1% of aconventional anionic aniline dye. It was then adjusted to pH 3.8 withformic acid. It was finally washed, mechanically set out and dried. Theleather obtained was very soft, supple, highly filled and uniform incolor.

EXAMPLE 22

Chrome tanned cattlehide leather which had a shaved thickness of 1.8 mmand had been adjusted to a pH of 5.0 and dyed with 0.7% of aconventional anionic aniline dye was drummed with 20% of the product ofExample 7, based on the shaved weight, at 40° C. for 1.5 hours.Thereafter the leather was adjusted with formic acid to a pH of 3.6 andfinished in a conventional manner. The leather thus obtained was verysoft and pliable.

EXAMPLE 23

Chrome tanned cattlehide leather which had a shaved weight of 1.8 mm andwhich had been adjusted to pH 5.0 and dyed with 0.7% of a conventionalanionic aniline dye was drummed with 15% of the product of Example 8,based on the shaved weight, at 40° C. for 30 minutes and then furthertreated with 3% of a conventional synthetic tanning agent for one hour.The leather was then adjusted with formic acid to pH 3.6 and finished ina conventional manner. The leather thus obtained had a pleasantly softand pliable feel.

EXAMPLE 24

The product of Example 9 was used as per the procedure described inExample 21. The leather thus obtained had soft and round handproperties.

EXAMPLE 25

The product of Example 10 was used as per the procedure described inExample 23. The leather thus obtained had a round, soft hand.

EXAMPLES 26 to 28

The products of Examples 11 to 13 were used as per the proceduredescribed in Example 22. The results were similar to those of thepreceding examples.

EXAMPLES 29 to 33

The products of Examples 14 to 18 were used as per the proceduredescribed in Example 21. The results were similar to those of thepreceding examples.

EXAMPLES 34 and 35

The products of Examples 19 and 20 were used as per the proceduredescribed in Example 23. The results were similar to those of thepreceding examples.

We claim:
 1. A process for fatliquoring and filling leather and furskins, which comprises treating leather with a polymeric fatliquoringagent, the polymers thereof consisting essentially of reaction productsofA) homo- or copolymers based on monoethylenically unsaturateddicarboxylic anhydrides, with the exception of sulfonated polymers, andobtainable by free-radically initiated polymerization of monomersconsisting essentially ofa) from 30 to 100 mol % of one or moremonoethylenically unsaturated dicarboxylic anhydrides of from 4 to 10carbon atoms, b) from 0 to 70 mol % of one or more aromatic vinylcompounds of the general formula I ##STR4## where R¹, R² and R³ are eachhydrogen, methyl or ethyl and k is 1 or 2, (c) from 0 to 70 mol % of oneor more vinyl esters of C₁ to C₄ -carboxylic acids, (d) from 0 to 50 mol% of one or more C₂ - to C₆ -olefins, and (e) from 0 to 30 mol % of oneor more monoethylenically unsaturated C₃ - to C₅ -carboxylic acids,which mixture of monomers (a) to (e) may additionally contain up to 10%by weight of further copolymerizable monomers, with B) amines of thegeneral formula R⁴ R⁵ NH, where R⁴ is hydrogen, C₁ - to C₂₀ -alkyl, C₅ -to C₈ -cycloalkyl or C₂ - to C₄ -hydroxyalkyl and R⁵ is C₆ - to C₃₀-alkyl, C₆ - to C₃₀ -alkenyl, C₁₅ -to C₈ -cycloalkyl or C₂ - to C₄-hydroxyalkyl, or alcohols of the general formula R⁶ --O--(C_(m) H_(2m)O)_(p) --(C_(n) H_(2n) O)_(q) --H, where R⁶ is C₁ - to C₃₀ -alkyl, C₂ -to C₃₀ -alkenyl, C₅ - to C₈ -cycloalkyl or--if p+q>0--hydrogen, m and nare each from 2 to 4 and p and q are each from 0 to 50, or mixtures ofsuch amines and alcohols; to form carboxamide or carboxylic ester ormixed carboxamide and carboxylic ester-containing polymers.
 2. A processas set forth in claim 1 wherein the reaction products were preparedusing as component A a homopolymer of a monoethylenically unsaturateddicarboxylic anhydride of from 4 to 10 carbon atoms (a).
 3. A process asset forth in claim 1 wherein the reaction products were prepared usingas component A a copolymer of monomers consisting essentially of(a) from30 to 99 mol % of a monoethylenically unsaturated dicarboxylic anhydrideof from 4 to 10 carbon atoms, and (b) from 1 to 70 mol % of one or morearomatic vinyl compounds I.
 4. A process as set forth in claim 1 whereinthe reaction products were prepared using as component A a copolymer ofmonomers consisting essentially of(a) from 30 to 99 mol % of amonoethylenically unsaturated dicarboxylic anhydride of from 4 to 10carbon atoms, and (c) from 1 to 70 mol % of one or more vinyl esters ofC₁ - to C₄ -carboxylic acids.
 5. A process as set forth in claim 1wherein the reaction products were prepared using as component A acopolymer of monomers consisting essentially of(a) from 50 to 99 mol %of a monoethylenically unsaturated dicarboxylic anhydride of from 4 to10 carbon atoms, and (d) from 1 to 50 mol % of one or more C₂ - to C₆-olefins.
 6. A process as set forth in claim 1 wherein the reactionproducts were prepared using maleic anhydride as monomer (a) for polymerA.
 7. A process as set forth in claim 1 wherein the reaction productswere prepared using as component B amines where R⁴ is hydrogen and R⁵ isC₁₀ - to C₂₂ -alkyl or C₁₀ - to C₂₂ -alkenyl.
 8. A process as set forthin claim 1 wherein the reaction products were prepared using ascomponent B alcohols where R⁶ is C₁ - to C₂₂ -alkyl or C₁₀ - to C₂₂-alkenyl, m and n are each from 2 to 4 and p and q are each from 0 to35.